Hydrazine sulphonate



Patented Oct. 22, 1935 UNITED STATES PATENT OFFICE bach-on-the-Main,

Germany, assignors to General Aniline Works, Inc., New-York, N. Y., acorporation of Delaware No Drawing. Application December 29, 1932,

Serial No. 649,446. 1932 In Germany January 12,

4 Claims. (01. 260-124) The present invention relates to newhydrazine-sulphonates, more particularly it relates to compoundscorresponding to the following probable general formula:

wherein Y stands for alkyl, alkoxy or halogen.

These compounds are produced by acting with a reducing agent on thecorresponding 2.5-disubstituted 4-acylamino-benzene-l-diazo-sulphonicacids.

They are of a great value for the production of azo-dyestuffs. For thispurpose, they are advantageously first mixed. with combining componentscontaining a hydroxyor an o-alkali metal group, whereof the adjacentposition is capable of attaching an aryl azo group, provided thatneither of the dyestuil' components contains a group producingsolubility in water. The compositions of matter, thus produced, are thenbrought onto the fibers in the presence of an alkali and the goods, thustreated, are thereafter subjectedtoa steaming operation.

As combining components of the aforesaid kind may be named:2-hydroxynaphthalene, its-nuclear substitution products as, forinstance, aroylamino hydroxynaphthalenes, (2hydroxynaphthalene-3-carbonyl) -amino-aryls (as described in U. S.Patents,N,0. 1,101,111 and No. 1,140,747), (6 halogenor6-arylamino-2-hydroxy-naphthalene-3-carbonyl)-amino-aryls (see GermanPatent No. 396,519 and British Patent No. 330,349), derivatives ofl-hydro-xy-naphthalene-4-carboxylic acid (see U. S. Patent No.1,453,660), as, for instance, l-hydroxy-naphthalene 4phenyl-ketone;-compounds. containing an acidic methylene group capableof being combined with diazocompounds, as,'for instance, pyrazolones andderivatives of fl-ketonaldehyde, for instance, acetoacetyl-amino-arylsand di- (aceto-acetyl-amino) aryls (see U. S. Patents No..'1 .594,864,No. 1,594,866, No. 1,594,867, No. 1,580,709, No. 1,634,090),dihydroxy-quinolines (see U. S. Patents No. 1,820,039, No. 1,846,073andNo. 1,846,074, British Patent No. 332,940),(2-hydroxy-carbazole-3-carbonyl) -amino-aryls,"(2 hydroxy benzocarbazole-3-carbonyl) -amino-aryls, (2 hydroxy anthracene-3-carbonyl)-amino-aryls.

The hydrazinesulpho'nate and the coupling .component, or an alkali metalsalt of the latter,

may be ground together and this mixture may be applied in an alkalinemedium to the fiber. The dyeing preparations yield under theseconditions, by steaming only, insoluble azo-dyestuffs on the Suchapplication to the fiber may consist in dyeing according to the one-bathmethod, or in printing; the dye-bath or the printing paste, or even thedyeing preparations themselves in powder form, are advantageously mixedwith the usual dyeing or printing assistants having wetting, emulsifyingor solvent properties, or also with the additional agents customarilyused in nitrosamine-printing colors, such. as, for example, chromate.

The following examples serve to illustratethe invention, but they arenot intended to limit it thereto, the parts being by weight:

(1) 225 parts of the sodium salt of 4-benzoylamino 2.5dimethoxybenzene-l-diazo sulphonic acid of 87.05% strength are suspendedin 3000 parts .of acetic acid of 3% strength, the whole is heated to iC. to C. and at this temperature 150 parts of zincdust are slowlyintroduced. When the mass has-become dissolved and decolorized, it isrendered alkaline by means of sodium carbonate, filtered by suctionwhile hot, sodium chloride is added and the product worked up as usual.There are thus obtained 385 parts of a feebly yellow press cake of thesodium salt of 4-benzoylamino-2.5dimethoxybenzene-l-hydrazine-sulphonicacid containing,58.35% of the pure substance.

It corresponds to the following formula:

(2) 394 parts of thesodium salt of 4-benzoylamino-Z-chloro-Smethoxybenzene-l-diazosulphonic acid are suspended in a solution ofparts of calcined sodium carbonate in 4000 parts of water, parts ofsodium-hydrosulphite are added thereto and the whole .is heated in thecourse of hour to 60 C. to 65 C. This temperature is maintained untilthe mass has become decolorized, indicating complete reduction.Thereupon, the Whole is heated-to 8 5 C. to 90 C., filtered by suction,sodium chloride is added to the filtrate and the product is worked'up'as usual. There are obtained 1222 parts of a nearly colorless paste ofthe sodium salt of 4-benzoylg amjno-2-chloro-S-methoxybenzene 1hydrazine sulphonic acid containing 19.36% of the pure substance. 7

It corresponds to the following formula:

Q-OO-NHQNlEb-NH-SOr-Na V V V o1 V 4r--( phenoxy-acetyl-amino Q 2,5-dimethoxybenzene-l-diazosulphonic acid,

.dimethoxybenzene-l-diazosulphonic acid,4-benzoylamino-2,5-dimethylbenzene-l-diazosulphonic acid,4-benzoylamino2-methyl-5-ch1orobenzene- 1 -diazosulphonic acid, a

4-(01- or p-naphthoylamino)-2-methoxy@-5-methylbenzene-l-diazosulphonicacid,4-benzoylamino-2-cho1oro 5 methylbenzene-ldiazosulphonic acid,

I 2.5-dimethoxy-benzene-l-diazosulphonic acid, 4-(2'-chlorobenzoylamino) -2,5-diethoxybenzene- .1 :diazosulohom'c acid,

. miibl'otolmmmo-i-i-li-idzlcisuiplrxlmci a cadirl,

4 nb-ireimasmlnlpironalmnir-r ll-.5 ,-5(l: dihtnorbelnmnzer-1 1 lll-aiiasmlnlpmin Lei mil 5 imdi i.

1 1 1 3 )E iildzleanelal: 5: wins :1 )',J :tsiislei El :1 n waddle r021: nl 1H o fltitjti ftllll l'iihi etenmwiofcii itiimimtssnioexaminer-emu 4-.(4K-methylbenzene- 1"-sulphonylamino) 2,5

4- 3'-methoxy-naphthalene-2Gcarbonylamino) Caustic soda solution of 34 B30 7 Water -1 273 Starch tragacanth-thickening 500 Sodium chromatesolution (1:4) 20 is printed on the material; the material is then 5dried, steamed for 10 minutes in a Mather-Flatt apparatus; rinsed hot,soaped and rinsed again.

, A violet print is thus obtained.

(5) 60 parts of the sodium salt of 4-benzoy1- 10 amino 2.5dimethoxybenz'ene-l-hydrazine-sulphonic acid of 58.35% strength,obtainable as de-. scribed in Example 1,10 parts of anhydrous sodiumacetate and 30 parts of Z-hydroxyanthracene 3 carbonyl-(l-amino-Z-methylbenzene are ground to form a homogeneous powder. 7 Thereare obtained 100 parts of dyestuff preparation.

A printing paste which contains:

. Parts 2 The above dyestuff preparation 1 u .50 Thiodiglycol Causticsoda solution of 34 B. 1 35' Water 375 Neutral starchtragaeanth-thickening 500 Sodium chromate solution (1:4) 20 is printedon the material and the goods are treated as indicated in Example 4.

A bluish-green print is obtained. By using, instead of2'-hydroxy-anthracene- 3 -carbonyll-amino-Z-methylbenzen'e)3-benzoylamino-2-hydroxynaphthalene, a violet print. is obtained.

(6) A printing paste which contains:

A slimming:sittetaccmmininmg: i i

new? i: :is; nirrmtla i m d I 1th a ante-teal m 72(11 1: hall a; (moist"are v'ov'ccelcofli 1 19:: not elzesclniitk dl:: mfiazmpl o le. l. V

l 1. r ar'ielldlis-wiviele t [lilffil its .tt'ilst s tofatuiniu l l l 1r'g'iism g1 toklr 2h ytqmimn'n .eulnlnnozo la :adi 's admit: i and: in ihere 13 250,?! o: ntonqrmntst it no 1 1 rpnossss: mm We: a amounted: i11' m a 1mm Mariel-snow 1 i2 )1 d haltet ,1 e-le; mirth $411Kitltnoiregroliningxeimpimlas. 7 Mi" The following table indicates theshades of a series of other dyeings or prints obtained in an yellowishto brownish powders and are valuable intermediates for the production ofazo dyestuffs.

Sodium salt of 4-benzoyl-amino-2,5-diethoxybenzene-1- hygrazinesulphonic acid.

Do Sodium salt of 4-acetyl-amino-2,5-diu1ethoxy-benzene-l-l1ydrazinesulphonic acid.

Do Do Sodium salt of 4-(pl1enoxy-acetylamino)- begzene-l-hydrazinesulphonic acid.

hylbenzene-l-sulphonyl:amino)-2,5-

Z-hydroxynanhthalnna 3-methy1-1-phenyl-5-pyrazolone1-l1ydroxynaphthalene-4-phenylketone V2-hydroxy-carbazole-3-carbonyl-(1-amin0-4-chlorobenzene)3-benzoylamino-2-hydroxynaphthalene4,4-di-(acetoacetyl-amino)-3,3-dimethyl-diphenyl Brownish violet.

Brownish-orange.

iolet.

Do. Yellowish-orange.

2,3,-hydroxynaphthoyl-(1-amino-2-methoxy-benzene) Redjgish-blue. 0.

4,4-di)-(acetoacetyl-amino)-3,3-dimethyl-diphenyl g fgfiggish-orange.Q55 1]giifiififififitiififli 51558 i-iiltliiy nhtfiih Reddish-blue.

zene 2,3-hydroxynaphthoyl-(l-amino-Z-ethoxybenzene) Blue.4,4-di-(acetoacetyl-amino)-3,3-dimethyl-diphenyl Orange.2,3-hydroxynaphthoyl-aminobenzene Reddish-vlolet.

dinlethoxy-benzene-l-hydrazine sulphonic acld.

analogous manner:

We claim:

1. The hydrazine sulphonates corresponding to the general formula:

wherein Z means an acyl radical of the lower aliphatic series or of thearomatic isocyclic series and Y stands for alkyl, alkoxy or halogen,which compounds represent when dry yellowish to brownish powders and arevaluable intermediates for the production of azo dyestuffs.

2. The hydrazine sulphonates corresponding to the general formula:

wherein R represents a radical of the aromatic isocyclic series and Ystands for alkyl, alkoxy or halogen, which compounds represent when dry3. The hydrazine sulphonates corresponding to the general formula:

alkyl wherein the benzene nucleus I may be substituted by alkyl, alkoxyor halogen and Y means alkyl, alkoxy or halogen, which compoundsrepresent when dry yellowish to brownish powders and are valuableintermediates for the production of azo dyestuffs.

4. The 4-benzoylamino 2,5 dimethoxy benzene-1-hydrazine-su1phonate ofthe formula:

which compound represents a feebly yellow powder and is a valuableintermediate for the production of azo dyestufis.

ARTHUR ZITSCHER. WILHELM SEIDENFADEN.

